In vivo insecticidal activity of cyclopentanespiro-5

НАУЧНИ ТРУДОВЕ НА РУСЕНСКИЯ УНИВЕРСИТЕТ - 2013, том 52, серия 10.2
In vivo insecticidal activity of cyclopentanespiro-5-hydantoin and its
two derivatives towards Mealy plum aphid (Hyalopterus pruni) and their
effect on Prunus cerasifera
Donyo Ganchev, Marin Marinov, Milena Zlateva, Rumyana Prodanova, Angel Nikolov,
Stefan Krustev, Neyko Stoyanov
In vivo insecticidal activity of cyclopentanespiro-5-hydantoin and its two derivatives towards
Mealy plum aphid (Hyalopterus pruni) and effect on Prunus cerasifera: The paper presents in vivo
insecticidal activity of cyclopentanespiro-5-hydantoin, cyclopentanespiro-5-(2,4-dithiohydantoin) and 1aminocyclopentanecarboxylic acid towards Mealy plum aphid (Hyalopterus pruni) and their effect on Prunus
cerasifera. It was found out that all the compounds exhibit excellent insecticidal action against the aphid. The
tested compounds do not manifest any deleterious effects towards plant Prunus cerasifera.
Key words: Cyclopentanespiro-5-hydantoin,Cyclopentanespiro-5-(2,4-dithiohydantoin), 1-Aminocyclo
pentanecarboxylic acid, Mealy plum aphid (Hyalopterus pruni), Prunus cerasifera.
INTRODUCTION
The Mealy plum aphid (Hyalopterus pruni) is a typical pest that infests plants of
Prunus spp., mainly plums, but also peaches, apricots and almonds. When infestation
occurs on young leaves in large numbers, it can cause significant feeding damage
combined with excreting honeydew onto lower leaves which become dark with sooty
moulds that grow in the resulting sticky film. These fungi reduce the plant's ability to
photosynthesize. Hyalopterus pruni is also a vector of plum pox potyvirus (PPV) [1].
In the current study we investigate the insecticidal action of cyclopentanespiro-5hydantoin, cyclopentanespiro-5-(2,4-dithiohydantoin) and 1-aminocyclopentanecarboxylic
acid towards Mealy plum aphid as well as the effect of these substances on the main
infected plant species - Prunus cerasifera, an appreciated widespread plant in Bulgaria of
economic significance.
EXPERIMENTAL
Synthetic compounds
The cyclopentanespiro-5-hydantoin (Fig. 1, a) was synthesized via the Bucherer-Lieb
method [2]. The cyclopentanespiro-5-(2,4-dithiohydantoin) (Fig. 1, b) was synthesized in
accordance with Marinov et al. [3]. The 1-aminocyclopentanecarboxylic acid (Fig. 1, c) was
obtained in accordance with Stoyanov and Marinov [4].
The products obtained were characterized through physicochemical parameters, IR
and NMR spectral data. The results obtained from these analyses are identical with those
previously published in the literature [4-6].
Cyclopentanespiro-5hydantoin
(CPSH)
a)
Cyclopentanespiro-5(2,4-dithiohydantoin)
(CPSDTH)
b)
Fig. 1
1-Aminocyclopentanecarboxylic acid
(ACPCA)
c)
Saturated concentrations of the compounds in water were as follows: CPSH – 1 %,
CPSDTH – 0.025 %, ACPCA – 0.1 %.
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НАУЧНИ ТРУДОВЕ НА РУСЕНСКИЯ УНИВЕРСИТЕТ - 2013, том 52, серия 10.2
In vivo tests
A branch of in vivo insecticidal test [7] was performed in order to establish the
insecticidal activity of tested compounds and their effect on infested plant species.
Ten different concentrations were tested to determine LC05 (NOEL), LC25 (LOAEL),
LC50 and LC90. Each test variant consisted of five replications. The individuals of each
variant were sprayed with a solution of the tested product in the tested concentration by
using a laboratory sprayer with a delivery rate 1000 l ha-1. Mortality was observed after 24
and 48 h. Effectiveness was calculated using Abbott’s formula [8].
The data received from the tests conducted was statistically manipulated with R
language for statistical computing [9] and drc R language package [10].
Standard phytotoxicity tests were conducted in accordance with OECD Guide 227 Terrestrial Plant Test: Vegetative Vigour Test [11]. The test period was 7 days. The plants
were weekly observed for visual phytotoxicity manifestations (necrosis, chlorosis,
whitening, deformations). On this basis, Percentage Disease Indexes (PDIs) were
calculated in a 5-grade scale [12]. Based on the PDIs, LC05 (NOEL), LC25 (LOAEL), LC50
were determined through the use of R language and drc package. The chemotherapeutic
indexes were calculated as a ratio between LC50 obtained from phytotoxicity test and LC90
obtained from insecticidal test.
RESULTS AND DISCUSSION
The spirohydantoins mentioned above were chosen for the current study due to their
biological activity [3, 13, 14]. Furthermore, complex compounds based on
cyclopentanespiro-5-hydantoin and its dithioanalogue have been synthesized to
investigate their potential biological or other properties [15, 16].
The dose-response curves from the insecticidal tests conducted with the compounds
(CPSH, CPSDTH and ACPCA) are depicted on figures 2 to 4.
Fig. 2
Established toxicological indicators of CPSH are:
1. NOAEL (No Observed Adverse Effect Level) LC05 = 0.031 %;
2. LOAEL (Lowest Observed Adverse Effect Level) LC25 = 0.042 %;
3. LC50 = 0.052 %;
4. LC90 = 0.075 %.
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НАУЧНИ ТРУДОВЕ НА РУСЕНСКИЯ УНИВЕРСИТЕТ - 2013, том 52, серия 10.2
Fig. 3
Established toxicological indicators of SPSDTH are:
1. NOAEL (No Observed Adverse Effect Level) LC05 = 0.00012 %;
2. LOAEL (Lowest Observed Adverse Effect Level) LC25 = 0.00027 %;
3. LC50 = 0.00047 %;
4. LC90 = 0.0011 %.
Fig. 4
Established toxicological indicators of ACPCA are:
1. NOAEL (No Observed Adverse Effect Level) LC05 = 0.0007 %;
2. LOAEL (Lowest Observed Adverse Effect Level) LC25 = 0.0017 %;
3. LC50 = 0.002 %;
4. LC90 = 0.007 %.
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НАУЧНИ ТРУДОВЕ НА РУСЕНСКИЯ УНИВЕРСИТЕТ - 2013, том 52, серия 10.2
The trials conducted for phytotoxicity, as per infested plant Prunus cerasifera, reveal
that in saturated concentrations in water, tested compounds do not manifest any
deleterious effects.
Chemotherapeutic indexes obtained for the compounds are as follows: 13.33 for
CPSH, 53.19 for CPSDTH and 14.28 for ACPCA.
The current study shows an excellent insecticidal action of cyclopentanespiro-5hydantoin, cyclopentanespiro-5-(2,4-dithiohydantoin) and 1-aminocyclopentanecarboxylic
acid. The minimal effective concentration (LC90) was between 0.0011 and 0.075 %. The
standard used – Karate Zeon 5 CS with active substance Lambda cyalotrin (3A MoA), was
effective against the aphid at 0.0015 % according to the active substance. LC90 of
SPSDTH for example was 0.0011 %.
REFERENCES
[1] http://www.rothamsted.ac.uk/insect-survey/STHyalopterus_pruni.html.
[2] Bucherer,H.T., V.Lieb. Über die bildung substituierter hydantoine aus aldehyden
und ketonen. Synthese von hydantoinen. J. Prakt. Chem., 1934, 141, 5-43.
[3] Marinov,M., D.Ganchev, P.Marinova, S.Krustev, N.Atanasova, M.Zlateva,
N.Stoyanov. Synthesis of cyclopentanespiro-5-(2,4-dithiohydantoin) and in vitro
insecticidal activity against Cladius pectinicornis. Bulg. J. Agric. Sci., 2012, 18, 929-933.
[4] Stoyanov,N., M.Marinov. Two methods for spirothiohydantoin synthesis. Acta
Chim. Slov., 2012, 59 (3), 680-685.
[5] Enchev,V., N.Stoyanov, V.Mateva, J.Popova, M.Kashchieva, B.Aleksiev,
M.Mitewa. Copper (II) complexes of spirohydantoins. Synthesis, quantum-chemical, and
spectroscopic study. Struct. Chem., 1999, 10 (5), 381-385.
[6] Marinov,M., S.Minchev, N.Stoyanov, G.Ivanova, M.Spassova, V.Enchev.
Synthesis, spectroscopic characterization and ab initio investigation of thioanalogues of
spirohydantoins. Croat. Chem. Acta., 2005, 78, 9-16.
[7] Haverty,M., J.Robertson. Laboratory bioassays for selecting candidate
insecticides and application rates for field test on the western spruce budworm. J. Econ.
Entomol., 1982, 75 (2), 179-182.
[8] Abbott,W.S. A method for computing the effectiveness of an insecticide. J. Econ.
Entomol., 1925, 18, 367-271.
[9] R Core Team. R: A language and environment for statistical computing. R
Foundation for Statistical Computing, Vienna, Austria, 2011. ISBN 3-900051-07-0, URL
http://www.R-project.org/.
[10] Ritz,C., J.C.Streibig. Bioassay analysis using R. J. Statist. Software, 2005, Vol.
12, Issue 5.
[11] OECD Guide 227 - Terrestrial Plant Test: Vegetative Vigour Test, 2006.
[12] McKinney,H.H. A new system of grading plant diseases. J. Agric. Res., 1923, 26,
195-218.
[13] Oldfield,W., C.H.Cashin. The chemistry and pharmacology of a series of
cycloalkanespiro-5-hydantoins. J. Med. Chem., 1965, 8, 239-250.
[14] Marinov,M., D.Ganchev, A.Nikolov, P.Marinova, S.Krustev, V.Madzharova,
N.Stoyanov. In vitro fungicidal activity of cyclopentanespiro-5-hydantoin and its derivatives
towards Blumeria graminis f. sp. tritici. Agric. Sci., 2013, 12, 97-101.
[15] Ahmedova,A., P.Marinova, G.Tyuliev, M.Mitewa. Copper complexes of two
cycloalkanespiro-5-dithiohydantoins: Synthesis, oxidation states and characterization.
Inorg. Chem. Commun., 2008, 11, 545-548.
[16] Marinova,P., M.Marinov, N.Stoyanov. New metal complexes of
cyclopentanespiro-5-hydantoin. Trakia J. Sci., Series Biomedical Sciences, 2012, 10 (1),
84-87.
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НАУЧНИ ТРУДОВЕ НА РУСЕНСКИЯ УНИВЕРСИТЕТ - 2013, том 52, серия 10.2
Acknowledgement
Financial support by the Agricultural University – Plovdiv, Bulgaria (Contract 06-12) is
gratefully acknowledged.
We are grateful also to Mr. G. Marinov, Sofia, for stimulating discussions.
About the authors:
Donyo Ganchev, PhD, Faculty of Plant Protection and Agroecology, Agricultural
University – Plovdiv, е-mail: donyo@abv.bg.
Marin Marinov, PhD, Faculty of Plant Protection and Agroecology, Agricultural
University – Plovdiv, е-mail: m_n_marinov@abv.bg.
Milena Zlateva, student, Faculty of Plant Protection and Agroecology, Agricultural
University – Plovdiv, е-mail: a_v_r_i_l@abv.bg.
Rumyana Prodanova, Assist. Prof., Faculty of Plant Protection and Agroecology,
Agricultural University – Plovdiv, е-mail: ru_prodanovakam@abv.bg.
Angel Nikolov, Assoc. Prof., PhD, Faculty of Plant Protection and Agroecology,
Agricultural University – Plovdiv, е-mail: nikolaev_au@abv.bg.
Stefan Krustev, Assoc. Prof., PhD, Faculty of Plant Protection and Agroecology,
Agricultural University – Plovdiv, е-mail: krust@abv.bg.
Neyko Stoyanov, Prof., PhD, Department of Chemistry and Chemical Technology,
University of Ruse – Razgrad Branch, e-mail: nstoianov@uni-ruse.bg.
This paper has been reviewed
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НАУЧНИ ТРУДОВЕ НА РУСЕНСКИЯ УНИВЕРСИТЕТ - 2013, том 52, серия 10.2
РУСЕНСКИ УНИВЕРСИТЕТ „АНГЕЛ КЪНЧЕВ”
UNIVERSITY OF RUSE „ANGEL KANCHEV“
ДИПЛОМА
Програмният комитет на
Научната конференция РУ&СУ’13
награждава с КРИСТАЛЕН ПРИЗ
“THE BEST PAPER”
Доньо Гънчев, Марин Маринов, Милена Златева,Румяна
Проданова, Ангел Николов, Стефан Кръстев,Нейко Стоянов
автори на доклада
In vivo инсектицидна активност на циклопентанспиро-5 хидантоин и две негови производни спрямо Прашеста сливова
листна въшка (Hyalopterus pruni) ефект към Prunus cerasifera
DIPLOMA
The Programme Committee of
the Scientific Conference RU&SU'13
Awards the Crystal Prize "THE BEST PAPER"to
Donyo Ganchev, Marin Marinov, Milena Zlateva,Rumyana
Prodanova, Angel Nikolov, Stefan Krustev,Neyko Stoyanov
authors of the paper
“In vivo insecticidal activity of cyclopentanespiro-5-hydantoin
and its two derivatives towards Mealy plum aphid
(Hyalopterus pruni) and their effect on Prunus cerasifera“
РЕКТОР
RECTOR
проф. д.т.н. Христо Белоев
Prof. DSc Hristo Beloev, DHC
02.11.2013
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